CZ307189B6 - A method of production of catalysts of a perovskite structure, catalysts perovskite structure and their use for high temperature decomposition of N2O - Google Patents

Abstract

The present invention relates to a method of production of perovskite structure catalysts for high temperature decomposition of N₂O, the catalysts having a general formula A_1-xB_xC_yD_1-yO_3-δ and wherein A and B are selected from the group consisting of lanthanides, alkaline earth metals, Group III.A and IV.A metals, transition metals of groups IB, II.B, III.B, IV.B, VI.B, VIII.B and Bi; C and D are selected from the group consisting of transition metals of Groups IV.B, V.B, VI.B, VII.B, VIII.B, Lanthanides, Sn, Al and Sb; x and y are independent numbers ranging from 0 to 1, and δ is the oxygen non-stoichiometric number of values ranging from -0.1 to 0.5; which comprises the steps of mixing of solid phases of water-soluble salts of cations A, B, C and D with a water soluble anionic salt selected from the group comprising carbonate, bicarbonate, oxalate, sulfate, metaphosphate, phosphate, hydroxide, nitrite, chromate and dichromate; homogenization; addition of surfactant; stirring; suspension filtration, drying and calcination.

The present invention further relates to catalysts of perovskite structure and use thereof for high temperature decomposition of N₂O.

Description

Technical field

The present invention relates to a process for the production of perovskite structure catalysts for high temperature N ₂ O decomposition. The invention solves total elimination of nitrous oxide on perovskite catalysts at high temperatures in a gas mixture corresponding to the composition below Pt-Rh sieves during oxidation of ammonia to NO in nitric acid plants. The invention describes the synthesis processes of the catalysts, their characterization and the catalytic effect under the conditions of a nitric acid production plant (at temperatures above 700 ° C and a gas flow rate corresponding to GHSV of 100,000 h ^-1 ). Furthermore, the invention relates to perovskite structure catalysts and their use for high temperature N ₂ O decomposition.

BACKGROUND OF THE INVENTION

Nitrous oxide (N ₂ O) is very often an undesirable product of combustion processes, in cars, heating plants, incinerators, chemical plants, etc. The reason for efforts to suppress its production is its ability to decompose ozone, which makes it a greenhouse gas, which is approximately 310x worse than CO ₂ (Global Warming Potential GWP = 310) in 100 years. For this reason, the effort is to reduce or completely suppress N ₂ O emissions.

One of the permanent producers of undesirable N ₂ O is the production of nitric acid, which produces nitrous oxide as an undesirable product in the incomplete oxidation of ammonia according to equation (I):

NH ₃ + 2 O ₂ h> N ₂ O + 3 H ₂ O (I)

Therefore, it is very important to find suitable catalysts to eliminate the resulting N ₂ O.

Existing nitric acid production technologies offer 3 possible ways of N ₂ O elimination at the primary, secondary or tertiary stage of the technology. The removal of N ₂ O at the primary stage requires a catalyst that would prevent the initial formation of N ₂ O during the combustion of ammonia on Pt / Rh catalyst networks, which has not been achieved so far. The secondary stage offers the use of a space directly below the Pt / Rh screens to accommodate the catalyst, which, however, has to withstand high temperatures and the specific composition of the corrosive gas produced by ammonia oxidation. The tertiary stage means the inclusion of an additional reactor, hence an investment, for placing the catalyst at the end of the HNO ₃ production technology and decomposing N ₂ O in the tail gas.

With regard to the design of existing nitric acid plants and the results of the research of catalysts for individual stages, the high temperature catalytic decomposition of N ₂ O into molecular oxygen and nitrogen directly below the Pt / Rh sieves at the so-called secondary stage seems to be the most suitable.

Catalysts based on metal oxides, supported metal oxides and ion exchanged metals in zeolites are known for the high temperature decomposition of N ₂ O.

Aluminosilicates are often used in catalytic reactions and these materials have also been tested for high temperature decomposition. DE 19805202 discloses for the decomposition of N ₂ O a cordierite-based catalyst doped with V, Cr, Fe, Ni, Co, Cu, Bi, Ca, Zn, Al, Mg operating at 800 to 1000 ° C, but without describing the preparation and the respective results of catalytic tests.

The zeolite ferrierite with Si / Al = 27.5 was subjected to an ion exchange in the ferrous sulfate solution in WO2012025630, and was tested at 850 ° C with a conversion of over 99%. However, the application of zeolite catalyst under industrial conditions requires high stability due to the rapid temperature rise and the catalytic functionality itself at temperatures in excess of 900 ° C. Due to

The high lifetime of H ₂ O in zeolite structures and the low thermal stability of ferrierite, the life of this catalyst is low, and is therefore completely unsatisfactory for industrial applications.

WO0202230 describes the use of cerium oxide as a catalytically active carrier (alumina and MgO are completely inert). The document discloses the synthesis and functionality of catalysts containing 0.1 to 10 moles of Co ( _{3 x} ) M _x O ₄ , where M is Fe or Al ax = 0-2, supported on CeO ₂ , Al ₂ O ₃ and MgO with possible 0.01 to 2 wt. ZrO ₂ . A comparison of catalysts operating at 900 ° C, 5 bar and GHSV = 55,000-110,000 h ^-1 indicates that the conversion of N ₂ O on the Co ₃ O ₄ -CeO ₂ catalyst 0.2% ZrO ₂ helps to reduce the degradation of catalyst activity over time , and is about 95% even after 100 days, while the Co ₂ AlO ₄ and Co ₂ AlO ₄ catalysts on the MgO carrier lose most of their activity after several days of operation. However, cobalt-containing catalysts are suspected to be a catalyst poison for Pt / Rh sieves and are therefore unsuitable for industrial nitric acid production applications.

US2009130010 discloses noble metal catalysts of Rh, Rh / Pd or Rh ₂ O ₃ on ZrO ₂ , Al ₂ O ₃ or TiO ₂ supports. However, the best working catalysts with 0.6% Rh are capable of decomposing only 80% of the N ₂ O resulting from the combustion of ammonia at 880 ° C.

Impregnation of cobalt and cerium with various impregnation processes on a ceramic base MgO-Al ₂ O ₃ fired at 1200 ° C leads to the preparation of catalysts having an activity of about 90% at 800 ° C according to US2010209325. Again, there is cobalt present, which could migrate to Pt / Rh networks and thereby reduce their catalytic activity.

The spinel disclosed in US6723295 was prepared by calcination of CuO, ZnO and Al ₂ O ₃ and its catalytic activity was monitored only at 750 ° C and showed a conversion of at most 68% after 21 days. The same 16-20-64% or 18-20-62% CuO-ZnO-Al ₂ O ₃ catalyst, which is the subject of WO2005000738 (A1), does not allow complete elimination of the N ₂ O formed in the off-gases even at 980 ° C .

By precipitation from iron and aluminum nitrate solutions, catalysts based on mixed oxides of Fe ₂ O ₃ with Al ₂ O ₃ were prepared in a paper by Giecko et al. (Giecko G., Borowiecki T., Gac W., Kruk L: Catalysis Today, 2008, 137, 403-9) giving a 95% N ₂ O conversion at 750 ° C.

Hexaaluminate catalysts (Santiago M., Pérez-Ramirez J .: Environ. Sci. Technol., 2007, 41, 1704-9) having the formula ABA1 _H O _W (where A = La, Ba, B = Mn, Fe, Ni), which were prepared by precipitation from a nitrate solution with ammonium carbonate. The authors reported the conversion of 95% N ₂ O at 830 ° C and GHSV = 30,000 mL / h g.

The La-Ni, La-Ni-Cu, La-Ni-Co metal-containing perovskite catalysts deposited on the honeycomb support WO2007104403 are capable of achieving a 95% conversion of N ₂ O to molecular nitrogen and oxygen at 900 ° C. However, the preparation of these catalysts again utilizes toxic ethylene glycol and is therefore not suitable for industrial applications. The use of toxic raw materials is not industrially applicable.

SUMMARY OF THE INVENTION

The present invention relates to perovskite-type catalysts, a process for their preparation and their use for high temperature decomposition of N ₂ O, wherein the production is carried out without the use of toxic ethylene glycol and is therefore suitable for industrial applications. This synthesis process is feasible on an industrial scale and guarantees the desired perovskite structure with a high catalytic effect when decomposing N ₂ O at high temperatures. The results of the catalytic tests confirm the complete elimination of N ₂ O at temperatures above 700 ° C in a gas mixture flow with a composition corresponding to

Ammonia combustion. Representatives of prior art catalysts were compared to prepared catalysts under identical conditions, and this testing confirmed the high efficiency of perovskite-type catalysts.

The present invention is a process for producing catalysts of the perovskite structure for high temperature decomposition of N ₂ O, having the general formula A | _ _x B _x C _y D _ly O3 g wherein A and B are selected from the group consisting of lanthanide metals, alkaline earth metals, metals of group III.A and IV.A, LB, II.B, III.B, IV.B, VI.B, VIII.B and Bi transition metals;

C and D are selected from the group consisting of transition metals of Group IV.B, Great, VI.B, VII.B, VIII.B, lanthanides, Sn, Al and Sb;

x and y are independent numbers ranging from 0 to 1 and δ is a number indicating the non-stoichiometry of oxygen ranging from -0.1 to 0.5;

which method comprises the following steps:

i) the solid phases of the water-soluble salts of cations A, B, C and D in a stoichiometric ratio are mixed with 1.1 to 1.4 times the water-soluble salt of an anion selected from the group consisting of carbonate, bicarbonate, oxalate, sulfate, metaphosphate, phosphate, hydroxide, nitrite , chromate and dichromate;

ii) homogenizing the resulting mixture;

iii) an aqueous surfactant solution having a concentration ranging from 5 to 80% (w / w) in an amount of up to 10% by weight is added to the homogenized mixture. % of the total weight of the homogenized salts of step ii), preferably 3 to 5 wt. % of the total weight of the homogenized salts, most preferably 4 wt. from the total weight of the homogenized salts, and the resulting mixture is stirred for 10 to 40 minutes, preferably for 20 minutes, to form a paste;

iv) the paste of step iii) is allowed to react by free standing at room temperature for at least two hours, preferably for 14 hours;

v) mixing the reacted paste of step iv) in water to form a suspension, preferably the amount of water is at least five times the volume of the reacted paste;

vi) filtering the suspension from the previous step, optionally washing the solid phase further with water and optionally centrifuging, washing with water and optionally centrifuging several times;

vii) drying the solid phase of the preceding step at a temperature in the range of from 100 to 150 ° C, preferably for at least one hour;

(viii) The dried solid is ground to a powder and calcined at a temperature of at least 900 ° C for at least 2 hours.

A water-soluble salt of cations A, B, C and D, as well as a water-soluble salt of anion (anionic precipitant) selected from the group consisting of carbonate, bicarbonate, oxalate, sulfate, metaphosphate, phosphate, hydroxide, nitrite, chromate and dichromate, whose solubility in water is greater than 0.1 mol / L at 20 ° C.

The stoichiometric ratio of the solid phase of the water-soluble cationic salts is understood to be the ratio of the amount of individual reactants which completely reacts to a given perovskite-type catalyst, e.g. : 1: 2. The principle of manufacture is to mix salts of the respective water-soluble cations together with a stoichiometric excess of anion salts, forming a low-solubility salt with a cation having a solubility below 0.01 mol / L at 20 ° C. In this system of substances, with the addition of a small amount of water, the cation salt is partially dissolved and reacted immediately with the anion of the partially dissolved anionic precipitant to form a sparingly soluble substance. To facilitate partial dissolution and precipitation, a surfactant is added. The process can be described by the general equation (II), (1x) AX (aq) + xBX (aq) + yCX (aq) + (ly) DX (aq) + qMN (aq) + nH ₂ O (1) A ₍₁ . _x) B _x C _y D _{(1 y)} N _q . n H ₂ O (s) + q MX (aq) (II)

Wherein X is independently an anion forming with A, B, C or D a water-soluble salt as defined above, N is an anion selected from the group consisting of carbonate, bicarbonate, oxalate, sulfate, metaphosphate, phosphate, hydroxide, nitrite, chromate and dichromate, M is a cation forming an N water-soluble salt of MN as defined above.

The resulting soluble MX salts are then washed and filtered. The residual solid phase A (i_ _x) B _x C _y D (Iy) Nq.nH2O after drying is calcined at a temperature allowing crystal water and leakage of volatile components to form carbon cation perovskite structure. Thus, the basic condition of this process is the formation of an insoluble cationic salt that originally formed another soluble salt. The soluble cation salts must then come into contact with the partially dissolved salt of the anion which forms an insoluble salt with the cation when partially dissolved.

In a preferred embodiment of the process for producing perovskite structure catalysts for high temperature decomposition, N ₂ O is the lanthanide La and / or Ce, the alkaline earth metal is Mg, Ca and / or Sr, the transition metal of the LB group is Cu and / or Ag, the transition metal II.B the transition metal of group IV.B is Y, the transition metal of group IV.B is Ti and / or Zr, the transition metal of Group VI.B is Cr, Mo and / or W, the transition metal of VII.B The Group VIII transition metal is Fe, Co and / or Ni, a Group III metal. A is Al and / or TI and a Group IV metal. A is Ge, Sn and / or Pb. In a more preferred embodiment, A is selected from the group consisting of La, Ba, Zn, Ca, Zr, Cu, Cr, Y, Ce, Mg, Ti, Pb, Ag; B is selected from the group consisting of Sr, Cu, Co, Ge, Ni, Ti, Cd, La, Ce; C and D is selected from the group consisting of Mn, Al, Ce, Co, Sn, Sb, V, Fe, Zr, W, Mo.

Most preferably, the process for producing catalysts of the perovskite structure for high temperature decomposition of N ₂ O, the above method for producing substances selected from the group consisting of La _0, 5SR _{0 5} MnO ₃ Lamna _3, ZnO 5CU0 sA1O _3, Cao ₇ Cuq ₃ MnO ₃ Ζηθ ^ Ltd. sCeo ₂ May ₈ O ₃ , 5Coo 5Ce0 ₃ , LaGeo _i2 Feo _j8 0 ₃ , Cro. _{8 Nio> 2} CE0 ₃ Mgo5Sro ₅ Sn0 _{3 PbTio>} Miio _{2 8} 0 ₃ CEO SrosZrOs ^, ^ MgojCdo WCF BaMnO ₃ CuMnO ₃ YCOO ₃ ceco ₃ LASB _3; Yo jSro.sMnCb, MgTi ₀₂ Mn ₀₈ O ₃ , Ceo ^ Sroo ^ MnCE, T1VO ₃ La _0j 5Sr _{0 5} FeO ₃ , CaTi _{0> 8} Ce _{0 2} O ₃ , Ca ₀ , ₇ Ce ₀ , ₃ MnO ₃ , AgCe _{0 5 0} Mn ₅ O _3, Pb _{0, 2} Lao _J8 MO0 _3, especially Lao sSro sMnCh Lamna and _third

In a preferred embodiment, the homogenization time of the mixture in step ii) is at least 5 minutes, preferably 5 to 20 minutes.

In a preferred embodiment, the surfactant is selected from the group of non-foaming nonionic surfactants containing -OH or -NH ₂ end groups, including ethoxylated (C1-C12) aliphatic alcohols, ethoxylated (C1-C21) fatty acids, preferably (C1-C18) fatty acids, polyoxyethylenes, carboxylic acid esters (C1 to C20), polyethylene glycol esters, preferably the surfactant is polyethylene glycol having an M _w in the range of from 200 to 800, most preferably the surfactant is PEG 400.

The surfactant is in the form of a 5 to 80% (w / w) aqueous solution, preferably a 30 to 70% (w / w) aqueous solution, more preferably a 40 to 60% (w / w) aqueous solution.

The water-soluble salts of cations A, B, C and D are selected from the group consisting of inorganic acids, organic monocarboxylic, dicarboxylic and tricarboxylic (C1 to C10) acids, and (C1 to C4) alkoxide salts, preferably the water-soluble salts of cations A, B , C and D their sulfates, carbonates, halides, nitrates, phosphates, acetates, formates, citrates, oxalates, lactates, oxalates, ethoxides, most preferably the water-soluble salts of cations A, B, C and D their nitrates, sulfates, chlorides, phosphates and carbonates.

The water-soluble anion salt selected from the group consisting of carbonate, bicarbonate, oxalate, sulfate, metaphosphate, phosphate, hydroxide, nitrite, chromate and dichromate in step i) preferably has a cation selected from the group consisting of Na ⁺ , K ⁺ , NH ₄ ⁺ , more preferably is

Water soluble salt of sodium carbonate, ammonium carbonate, sodium oxalate, potassium oxalate or ammonium oxalate.

In another preferred embodiment of the process of the present invention, the solid phase drying step in step vii) is carried out at a temperature of 120 ° C, preferably for at least two hours.

In another preferred embodiment of the process of the present invention, the calcination in step viii) is carried out at a temperature in the range of 900 ° C to 1000 ° C, preferably at 950 ° C, more preferably for 4 hours.

The present invention is also a catalyst of the perovskite structure of the general formula A] _ _x B _x C _y Di _y O ₃ § for high temperature decomposition of N ₂ O, wherein A and B are selected from the group consisting of lanthanide metals, alkaline earth metals, metals of group III. A and IV.A, transition metals of Group IB, Π.B, II1.B, IV.B, VI.B, V1II.B and Bi;

C and D are selected from the group consisting of transition metals of Group IV.B, Great, VI.B, VII.B, VIII.B, lanthanides, Sn, Al and Sb;

and wherein x and y are independent numbers ranging from 0 to 1 and δ determines the non-stoichiometry of oxygen and takes values from -0,1 to 0,5, and wherein the substance of formula A | _x B _x C _y D | _ _y O _{3 s} is not BaMnO ₃ . CuMnO ₃ , YCoO ₃ , CeCoO ₃ , LaSbO ₃ , Yo ^ Sro.sMnCh, MgTio _{> 2} M8080 ₃ , Ceo ^ Sro 5MnO ₃ , T1VO ₃ , La ^ Sro ^ FeO · ;, CaTio.8Ceo _{> 2} 0 ₃ , Ca ₀ , ₇ Ce ₀ , ₃ MnO ₃ , AgCeo, ₅ Me, ₅ 0 ₃ , Pb _0j2 La _0j8 MoO ₃ .

In a preferred embodiment, the lanthanide is La and / or Ce, the alkaline earth metal is Mg, Ca and / or Sr, the transition metal of the IB group is Cu and / or Ag, the transition metal of Group II.B is Zn and / or Cd, the transition metal III Group B is Y, Group IV transition metal is Ti and / or Zr, Group VI.B transition metal is Cr, Mo and / or W, Group VII transition metal is Mn and Group VIII transition metal is Le, Co and / or Ni, the Group III.A metal is Al and / or T1, and the Group IV.A metal is Ge, Sn and / or Pb.

In a more preferred embodiment, A is selected from the group consisting of La, Ba, Zn, Ca, Zr, Cu, Cr, Y, Ce, Mg, Ti, Pb, Ag; B is selected from the group consisting of Sr, Cu, Co, Ge, Ni, Ti, Cd, La, Ce; C and D is selected from the group consisting of Mn, Al, Ce, Co, Sn, Sb, V, Fe, Zr, W, Mo.

In a preferred embodiment, the perovskite structure catalyst for high temperature decomposition of N ₂ O is selected from the group consisting of Lao, ₅ Sro ₅ MnO ₃ , LaMnO ₃ , Zn _{0 5} Cu _{0> 5} AlO ₃ , Cao _{> 7} Cuo, ₃ MnO ₃ , Zno 2. Ltd. Ceo ^ ^ ^ Well CFY ZrojCoo ^ Bohemia, LAGE ₂ Feo ^ 0 ₃ Cro8Nio ₂ CE0 _3, MgO Ltd. ^ ^ _i2 SNCF PbTio _Well; 80 _{3 5} Ceo jSro ZrO _3, MgO-CdojWOj.

In a most preferred embodiment, the catalyst of the perovskite structure is La _{0 5} Sr _{0 5} MnO ₃ and LaMnO ₃ .

The present invention also relates to the use of perovskite structure catalysts of the general formula A 1 _x B _x C _y D 1 _y O ₃ g according to the present invention wherein A and B are selected from the group consisting of lanthanides, alkaline earth metals, Group III metals. A and IV.A, Group IB, II.B, III.B, IV.B, VI.B, VIII.B and Bi transition metals;

C and D are selected from the group consisting of transition metals of Group IV.B, Great, VI.B, VII.B, VIII.B, lanthanides, Sn, Al and Sb;

and wherein x and y are independent numbers ranging from 0 to 1 and δ determines the non-stoichiometry of oxygen and takes values from -0.1 to 0.5, and wherein the compound of formula A _{x x} B _x C _in Di- _y 0, ₀ is not BaMnO ₃ , CuMnO _3; YCoO ₃ , CeCoO ₃ , LaSbO ₃ , Y ₀ , ₅ Sr ₀ , 5MnO ₃ , MgTi _{0; 2} Me, _g 0 ₃ , Ce ₀ , 5Sro _{> 5} MnO ₃ , T1VO ₃ , Lao, ₅ Sr _Oj 5FeO ₃ , CaTi _{0 0 8Ce; 2} O _3, Cao, Ce _{7 3} MnO ₃ AgCeo ₅ Well ₅ 0 _{3 0} Pb, La _{2 0 3} 8MoO;

for high temperature decomposition of N ₂ O. High temperature decomposition of N ₂ O means decomposition of N ₂ O at temperatures above 700 ° C, preferably at temperatures above 850 ° C, most preferably at temperatures above 900 ° C.

-5GB 307189 B6

The perovskite-type catalysts prepared by the process of the present invention are highly thermally stable and have long-term activity in decomposing nitrous oxide at temperatures in excess of 700 ° C under conditions corresponding to ammonia combustion in nitric acid production. The process does not contain toxic substances as known in the art, is economically advantageous and guarantees the desired perovskite structure, and can therefore be applied on an industrial scale.

Clarification of drawings

Figure 1: XRD diffractogram of the LSM-P1 catalyst prepared according to Example 1

Figure 2: XRD diffractogram of the LSM-P2 catalyst prepared according to Example 2

Figure 3: XRD diffractogram of the LSM-P3 catalyst prepared according to Example 3

Figure 4: XRD diffractogram of the LSM-P4 catalyst prepared according to Example 4

Figure 5: XRD diffractogram of the LSM-P5 catalyst prepared according to Example 5

Figure 6: XRD diffractogram of the LSM-P6 catalyst prepared according to Example 6

DETAILED DESCRIPTION OF THE INVENTION

Example 1: Preparation of La (Sr _{L5 (i5} MnOs of lanthanum chloride hexahydrate, in the presence of sodium carbonate

8.6 g of LaCl ₃ .7H ₂ O, 7.8 g of MnSO ₄ .H ₂ O, 4.9 g of Sr (NO ₃ ) ₃ and 32.9 g of Na ₂ CO ₃ .10H ₂ O were stirred in an automatic agate dish for 10 min. A 50% aqueous solution of polyethylene glycol PEG-400 was then added dropwise to form a paste (about 5 mL). This was stirred for another 20 min. The resulting intermediate was allowed to stand overnight in air and stirred the next day in water to form a slurry allowing transfer to centrifuge containers or transfer to a filter septum. This was followed by separation of the solid phase from the solution (centrifugation, filtration) and repeated washing with water and separation of the solid phase. This was dried at 120 ° C for 2 hours, pulverized and calcined at 950 ° C for 4 hours. The resulting catalyst La _0, 5SR _{0 5} MnO ₃ (LSM-designated P1) was pressure formed into pellets and used for the catalytic tests. The X-ray diffraction result of the prepared catalyst is shown in FIG. 1.

Example 2: Preparation of Lao fSrojMnOs from lanthanum chloride in the presence of sodium carbonate hexahydrate and anhydrous sodium carbonate

8.6 g of LaCl ₃ .7H ₂ O, 7.8 g of MnSO ₄ .H ₂ O, 4.9 g of Sr (NO ₃ ) ₃ and 16.5 g of Na ₂ CO ₃ .10H ₂ O and 6.1 g The ₂ CO ₃ was stirred in an automatic agate dish for 10 min. Subsequently was repeated according to Example 1 and the catalyst of La _0> 5Sro, 5Mn0 ₃ (designated LSM-P2). The X-ray diffraction result of the prepared catalyst is shown in FIG. 2.

Example 3: Preparation of Lao (Sro) from lanthanum carbonate in the presence of sodium carbonate hexahydrate and anhydrous sodium carbonate

5.5 g of La ₂ (CO ₃ ) ₃ .xH ₂ O, 7.8 g of MnSO ₄ .H ₂ O, 4.9 g of Sr (NO ₃ ) ₃ and 10.9 g of Na ₂ CO ₃ .10H ₂ O and 4.04 g of Na ₂ CO ₃ were stirred in an automatic agate dish for 10 min. It was then repeated

-6CZ 307189 B6 The procedure of Example 1 and the catalyst _{Lao> 5} Sro5Mn0 ₃ (designated LSM-P3). The X-ray diffraction result of the prepared catalyst is shown in FIG. 3.

Example 4: Preparation of _Sr-05 Lao Mn0 ₃ of lanthanum nitrate in the presence of sodium oxalate

10.0 g of La (NO ₃ ) ₃ .6H ₂ O, 7.8 g of MnSO ₄ .H ₂ O, 4.9 g of Sr (NO ₃ ) ₃ and 19.4 g of Na ₂ C ₂ O ₄ were homogenized in automatic agate dish for 5 to 10 min. A 50% polyethylene glycol PEG-400 solution (about 10 mL) was then added dropwise to form a paste. This was mixed for a total time with homogenization giving 30 min. The intermediate was left overnight in air and stirred the next day in water. The suspension was centrifuged and washed repeatedly with water and centrifuged. The resulting solid phase was dried at 120 ° C for 2 h, pulverized and calcined at 950 ° C for 4 h. The resulting catalyst Lao ^ Sro ^ MnCft (designated LSM-P4) was formed into granules by pressure and used for catalytic tests. The X-ray diffraction result of the prepared catalyst is shown in FIG. 4.

Example 5: Preparation of Lao ₅ Sr ₍ MnO ₃₎ from lanthanum nitrate in the presence of ammonium oxalate

5.0 g La (NO ₃ ) ₃ .6H ₂ O, 3.9 g MnSO ₄ .H ₂ O, 2.5 g Sr (NO ₃ ) ₃ and 8.2 g (NH ₄ ) ₂ C ₂ O ₄ was homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst Lao ₅ Sro _{> 5} MnO ₃ (designated LSM-P5). The X-ray diffraction result of the prepared catalyst is shown in FIG. 5.

Example 6: Preparation of LaMnO ₃ from lanthanum nitrate in the presence of sodium oxalate

17.3 g of La (NO ₃ ) ₃ .6H ₂ O, 6.8 g of MnSO ₄ .H ₂ O and 13.4 g of Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the LaMnO ₃ catalyst (designated LSM-P6). The X-ray diffraction result of the prepared catalyst is shown in FIG. 6.

Comparative Example 1: Preparation of a Rh / Al ₂ O ₃ catalyst (Rh / Al ₂ O ₃ -Spl)

The impregnation of rhodium on α-alumina was performed according to the patent EP 1586365 (Rh / Al ₂ O ₃ -SP1).

Comparative Example 2: Preparation of Cu-Ζη spin spinel catalyst (CZA - SP2)

Cu-Zn-Al spin (CZA-SP2) was prepared according to US2007 / 0098613A1 by calcination of CuO, ZnO and Al ₂ O ₃ .

Comparative Example 3: Preparation of 0.9% Fe naferrierite catalyst (Fe-FER-SP3)

A sample of the catalyst 0.9% Fe on ferrierite (Fe-FER-SP3), which complies with the claims in WO2012025630, was prepared as described in (Sadovska G., Tabor E., Sazama P., Lhotka M., Bernauer M ., Sobalík Z .: Cat. Com., 2017, 89, 133-137), i.e. by impregnating the granules of the parent zeolite (ferrierite, Si / Al = 22), dried for 4 hours at 120 ° C with FeCl ₃ in acetylcetone. After 12 h, the sample was air dried and subjected to vacuum decomposition for 1 h at 100 ° C and 3 h at 350 ° C. It was then cooled to room temperature, washed with distilled water and calcined for 12 hours at 450 ° C and 4 hours at 950 ° C.

Comparative Example 4: Preparation of a catalyst of 70% Fe ₂ O ₂ and 30% Al ₂ O ₂ (FeAl-SP5)

The mixed biphasic oxide containing iron and alumina (FeAl-SP5) was prepared according to the article (Giecko G., Borowiecki T., Gac W., Kruk J .: Catalysis Today, 2008, 137, 403-9).

Comparative Example 5: Preparation of LaFeAl / f Hexaaluminate Catalyst (LFA-SP6)

La-Fe-Al hexaaluminate (LFA-SP6) was prepared by precipitation from a solution of the metal nitrates as described (Santiago M., Pérez-Ramirez J .: Environ. Sci. Technol., 2007, 41, 1704-9).

Example Ί: Testing the efficiency of the catalyst of Example 1

A gas mixture of 1000 ppm N ₂ O, 0.5% NO, 2% O ₂ and 10% H ₂ O in He passed through the quartz reactor under a pressure of 1 bar, with a GHSV load of 100,000 h ¹ (contact time 0.003 s) via a catalyst bed containing catalyst Example 1. After reaching 900 ° C, it subsequently decreased after a 50 ° C step with isotherm at a given temperature for 1 h. The composition of the output mixture showed 100% elimination of N ₂ O over the entire temperature range.

Example 8: Testing the Efficiency of the Catalysts of Examples 2 to 6

The catalyst test described in Example 7 was applied to the other perovskite catalysts prepared in Examples 2 to 6, which also completely eliminated the presence of N ₂ O in the gas mixture under given conditions.

Example 9: Comparison of catalyst efficiency

The catalysts prepared according to Examples 1 to 6 as well as Comparative Examples 1 to 5 were subjected to catalytic tests in the same gas mixture of the same flow rate as in Example 7, but for a lower sample volume giving a higher GHSV load = 350,000 h ¹ (contact time) <0.001 s), which allows to detect differences in catalytic activity of individual catalysts. The temperature dependence of the N ₂ O conversion obtained are shown in Tables 1 to 4.

Example 10: Comparing the efficiency of the catalysts after 12 days of use

The catalysts of Comparative Examples 1 to 3 and the catalyst of Example 4 were subjected to a long-term load in a stream of ammonia combustion gas at 800 ° C for 12 days. The catalytic activity was again tested under the conditions given in Example 9. The resulting values are shown in Table 4. The data obtained show that the LSM-P4 catalyst prepared according to Example 4 still allows> 99% decomposition of unwanted N ₂ O at high temperatures and increased load. , which confirms its high temperature and catalytic stability.

-8GB 307189 B6

Table 1. Known catalysts prepared according to Comparative Examples 1 to 5.

Catalyst Ingredients Conversion (%) (GHSV = 350,000 h ^-1 ) 700 ° C 750 ° C 800 [deg.] C 850 ° C 900 ° C Rh / Al ₂ O ₃ -SPl 0.6% Rh on Al ₂ O ₃ 94 97 99 100 ALIGN! 100 ALIGN! CZA-SP1 ZnCuA104 65.2 89.9 98.2 99.6 100 ALIGN! Fe-FER-SP2 0.9% Fe to FER 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! FeA1-SP4 70% Fe 2 O 3 + 30% Al 2 O 3 2 9.6 27.3 58.3 87 LFA-SP5 LaFeAlnOig 2 5 11.1 35.9 69

Table 2. Catalytic properties of the Lao, 5Sr, _0.5 MnO ₃ catalyst prepared according to Examples 1 to 3

Catalyst Conversion (%) (GHSV = 350,000 h ¹ ) 700 ° C 750 ° C 800 [deg.] C 850 ° C 900 ° C LSM-P1 67.1 85.9 96.9 99.7 100 ALIGN! LSM-P2 51.7 84.5 95.7 100 ALIGN! 100 ALIGN! LSM-P3 30.4 58.5 85.3 96.3 100 ALIGN!

Table 3. Composition and catalytic properties of perovskite catalysts prepared according to

Examples 4 to 6

Catalyst Ingredients Conversion (%) (GHSV = 350,000 h ¹ ) 700 ° C 750 ° C 800 [deg.] C 850 ° C 900 ° C LSM-P4 La _0j 5Sro, ₅ Mn0 ₃ 95.7 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! LSM-P5 Lao _! 5Nr _{0> 5} Mn0 ₃ 15.5 34.2 54.4 79.1 93.9 LM-P6 LaMnO ₃ 29.8 58.3 84.9 94.1 100 ALIGN!

Table 4. Catalyst composition and catalytic properties after 12 days of use

Catalyst Ingredients Conversion (%) (GHSV = 350,000 h ¹ ) 700 ° C 750 ° C 800 [deg.] C 850 ° C 900 ° C Rh / Al ₂ O ₃ -SPl 0.6% Rh on Al ₂ O ₃ 73.7 84 93 97 99 CZA-SP1 ZnCuA104 65 85 95 98 99 Fe-FER-SP2 0.9% Fe to FER 91 94.5 97 98 98.6 LSM-P4 LaosSrosMnOs 72 95.5 99.2 100 ALIGN! 100 ALIGN!

-9EN 307189 B6

Example 11: Preparation of BaMnO ₃ in the presence of sodium oxalate

10.5 g Ba (NO ₃ ) ₂ , 6.8 g MnSO ₄ .H ₂ O and 13.4 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the BaMnO2 catalyst.

Example 12: Preparation of Zno.sCuo.sAlOs in the presence of sodium oxalate

9.9 g Zn (NO ₃ ) ₂ .6H ₂ O, 8.1 g Cu (NO ₃ ) ₂ .3H ₂ O, 25.0 g A1 (NO ₃ ) ₃ .9H ₂ O and 22.3 g Na ₂ C ₂ O ₄ was homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain a ZnO ₅ Cuo, 5AlO ₃ catalyst.

Example 13: Preparation of Cao-CuO.1MnOs in the presence of sodium oxalate

6.6 g Ca (NO ₃ ) ₂ .4H ₂ O, 2.9 g Cu (NO ₃ ) ₃ .3H ₂ O, 6.8 g MnSO ₄ .H ₂ O and 13.4 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure was repeated as in Example 4 and the catalyst Cao 7Cuo _J3 Mn0 _third

Example 14: Preparation of Zno.3Sro.5Ceo.2Mno.8O3 in the presence of sodium oxalate

7.4 g Zn (NO ₃ ) ₂ .6H ₂ O, 5.3 g Sr (NO ₃ ) ₂ , 4.3 g Ce (NO ₃ ) ₃ .6H ₂ O, 6.8 g MnSO ₄ .H ₂ O and 8.4 g of Na ₂ C ₂ O ₄ was homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure was repeated as in Example 4 and the catalyst Zn sSro ₀ ^ ^ Mno.sCh Ceo.

Example 15: Preparation of ZrO CoCo.jCeOj in the presence of sodium oxalate

3.2 g ZrOCl ₂ .8H ₂ O, 2.9 g Co (NO ₃ ) ₂ .6H ₂ O, 8.1 g Ce (SO ₄ ) ₂ .4H ₂ O and 7.2 g Na ₂ C ₂ O ₄ was homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst Zro2Co2SCeCl2.

Example 16: Preparation of CuMnO _s in the presence of sodium oxalate

9.7 g of Cu (NO ₃ ) ₂ .3H ₂ O, 6.8 g of MnSO ₄ .H ₂ O and 13.4 g of Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain a CuMnO ₃ catalyst.

Example 17: Preparation of LaGeo.2Feo.sO3 in the presence of sodium oxalate

8.7 g of La (NO ₃ ) ₃ .6H ₂ O, 0.9 g of GeCl ₄ , 6.5 g of Fe (NO ₃ ) ₃ .9H ₂ O and 6.7 g of Na ₂ C ₂ O ₄ were homogenized in automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst LaGe _{12 Fe 3 O 3} .

Example 18: Preparation of CroxN 10 AlCl 3 in the presence of sodium oxalate

6.4 g Cr (NO ₃ ) ₃ .9H ₂ O, 1.2 g Ni (NO ₃ ) ₂ · 6H ₂ O, 8.7 g Ce (NO ₃ ) ₃ .6H ₂ O and 6.7 g Na ₂ C ₂ O ₄ was homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure was repeated as in Example 4 and the catalyst of Cr _0, 8Nio ₂ CE0 _third

- 10GB 307189 B6

Example 19: Preparation of YCOO3 in the presence of sodium oxalate

7.7 g Y (NO ₃ ) ₃ .6H ₂ O, 5.8 g Co (NO ₃ ) ₂ .6H ₂ O and 6.7 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. . Subsequently, the procedure of Example 4 was repeated to obtain the YCoO ₃ catalyst.

Example 20: Preparation of CeCoCY in the presence of sodium oxalate

8.7 g Ce (NO ₃ ) ₃ .6H ₂ O, 5.8 g Co (NO ₃ ) ₂ .6H ₂ O and 6.7 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. . Subsequently, the procedure of Example 4 was repeated to obtain the CeCoO ₃ catalyst.

Example 21: Preparation of Sr ₅ mg of _{LL LL} SNO3 ₅ in the presence of sodium oxalate

3.8 g Mg (NO ₃ ) ₃ .6H ₂ O, 2.1 g Sr (NO ₃ ) ₂ , 4.1 g SnC ₂ O ₄ and 3.4 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate bowl after 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst Mo 2 S 2 S.snCl 2

Example 22: Preparation of LaShCf in the presence of sodium oxalate

8.7 g of La (NO ₃ ) ₃ .6H ₂ O, 4.6 g of SbCl ₃ and 6.7 g of Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst LaSbO ₃ .

Example 23: Preparation of Υ (> ^ _{Ι) 5} Μηθ3 in the presence of sodium oxalate

3.8 g Y (NO ₃ ) ₃ .6H ₂ O, 2.1 g Sr (NO ₃ ) ₂ , 3.4 g MnSO ₄ .H ₂ O and 6.7 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate bowl for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst Y _0.5Sr 0.5MnO ₃ .

Example 24: Preparation of MgTi (M ₂ O 3) 3 in the presence of sodium oxalate

5.1 g Mg (NO ₃ ) ₂ .6H ₂ O, 0.9 g Ti (OC ₂ H ₅ ) ₄ , 2.7 g MnSO ₄ .H ₂ O and 6.7 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the MgT 10 catalyst, ₂ Mn _0> 80 ₃ .

Example 25: Preparation of Ce _{3 S 3 O 3} MnO 3 in the presence of sodium oxalate

4.3 g Ce (NO ₃ ) ₃ .6H ₂ O, 2.1 g Sr (NO ₃ ) ₂ , 3.4 g MnSO ₄ .H ₂ O and 6.7 g Na ₂ C ₂ O ₄ were homogenized in automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain a catalyst.

Example 26: Preparation of TIVO ₃ in the presence of sodium oxalate

₃ T1VO 5.3 g, 3.2 g VC1 ₃ and 6.7 g Na ₂ C ₂ O ₄ were homogenized in an agate automatic mortar for 5 to 10 minutes. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst T1VO ₃ .

Example 27: Preparation of La ( ₃₃ Sr _{) 5} FeO ₃ in the presence of sodium oxalate

4.3 g Fa (NO ₃ ) ₃ .6H ₂ O, 2.1 g Sr (NO ₃ ) ₂ , 8.1 g Fe (NO ₃ ) ₃ .9H ₂ O and 6.7 g Na ₂ C ₂ O ₄ was homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst Eao. ₅ Ltd., 5Fe0 ₃ .

Example 28: Preparation of PhTiojMno nO ₃ in the presence of sodium oxalate

6.6 g Pb (NO ₃ ) ₂ , 0.9 g Ti (OC ₂ H ₅ ) ₄ , 2.7 g MnSO ₄ .H ₂ O and 6.7 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate bowl after 5 to 10 min. Subsequently, the procedure was repeated as in Example 4 and the catalyst PbTio _{2 Mn} O _{8 3rd}

Example 29: Preparation of Ce ₃ Sr ₍₁₃ ZrO ₃₎ in the presence of sodium oxalate

4.3 g Ce (NO ₃ ) ₃ .6H ₂ O, 2.1 g Sr (NO ₃ ) ₂ , 6.5 g ZrOCl ₂ .8H ₂ O and 6.7 g Na ₂ C ₂ O ₄ were homogenized in automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst Ce 50.5 _{S 5 5} ZrO ₃ .

Example 30: Preparation of CaTi ( _{) 3} Ceo, 20 ₃ in the presence of sodium oxalate

4.7 g Ca (NO ₃ ) ₂ .4H ₂ O, 3.7 g Ti (OC ₂ H ₅ ) ₄ , 1.7 g Ce (NO ₃ ) ₃ .6H ₂ O and 6.7 g Na ₂ C ₂ O ₄ was homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain a catalyst of CaTi _{0> 8} Ceo, ₂ 0 ₃ .

Example 31: Preparation of Ca ( ₁₇₎ Ceo. ₃ MnO ₃ in the presence of sodium oxalate

3.3 g Ca (NO ₃ ) ₂ .4H ₂ O, 2.6 g Ce (NO ₃ ) ₃ .6H ₂ O, 3.4 g MnSO ₄ .H ₂ O and 6.7 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain a CaojCeo, ₃ MnO ₃ catalyst.

Example 32: Preparation of AgCeo ₃ Mn _{1) 3} 0 ₃ in the presence of sodium oxalate

3.4 g AgNO ₃ , 4.3 g Ce (NO ₃ ) ₃ .6H ₂ O, 1.7 g MnSO ₄ .H ₂ O and 6.7 gNa ₂ C ₂ O ₄ were homogenized in an automatic agate dish for 5 to 6 hours. 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst AgCeo.5Mno.5O3.

Example 33: Preparation of Mg ₁₅ Cd _{< 13} WO ₃ in the presence of sodium oxalate

2.6 g Mg (NO ₃ ) ₂ .6H ₂ O, 3.1 g Cd (NO ₃ ) ₂ .4H ₂ O, 6.6 g Na ₂ WO ₄ .2H ₂ O and 6.7 g Na ₂ C ₂ O ₄ was homogenized in an automatic agate dish for 5 to 10 min. Subsequently, the procedure of Example 4 was repeated to obtain the catalyst Mgo 5 C to 5 WO 3.

Example 34: Preparation of Pb _{11 2} La () sMoO ₃ in the presence of sodium oxalate

1.3 g Pb (NO ₃ ) ₂ , 6.9 g Fa (NO ₃ ) ₃ .6H ₂ O, 2.6 g MoO ₂ and 6.7 g Na ₂ C ₂ O ₄ were homogenized in an automatic agate bowl after 5 to 10 min. MoO ₂ can also be used as finely ground or nanoparticle structures. Subsequently, the procedure was repeated as in Example 4 and the catalyst PbO 2LA ₀ 8Mo0 _third

Claims (10)

PATENT CLAIMS A process for producing perovskite structure catalysts for high temperature decomposition of N ₂ O having the general formula A! _x B _x C _y O ₃ Di _ _{y S,} and wherein A and B are selected from the group consisting of lanthanide metals, alkaline earth metals, metals from Group IIIA and IV.A, transition metal group IB, IIB, IIIB , IV.B, VI.B, VIII.B and Bi; C and D are selected from the group consisting of transition metals of Group IV.B, Great, VI.B, VII.B, VIII.B, lanthanides, Sn, Al and Sb; x and y are independent numbers ranging from 0 to 1 and δ is a number indicating the non-stoichiometry of oxygen ranging from -0.1 to 0.5; characterized in that it comprises the following steps: i) the solid phases of the water-soluble salts of cations A, B, C and D in a stoichiometric ratio are mixed with 1.1 to 1.4 times the water-soluble salt of an anion selected from the group consisting of carbonate, bicarbonate, oxalate, sulfate, metaphosphate, phosphate, hydroxide, nitrite , chromate and dichromate; ii) homogenizing the resulting mixture; iii) adding to the homogenized mixture an aqueous surfactant solution in a concentration ranging from 5 to 80 wt. % and up to 10 wt. % of the total weight of the homogenized salts of step ii), and the resulting mixture is stirred for 10 to 40 minutes to form a paste; iv) allowing the paste of step iii) to react by free standing at room temperature for at least two hours; v) mixing the reacted paste from step iv) in water to form a suspension; vi) filtering the suspension from the previous step, optionally washing the solid phase further with water and optionally centrifuging, washing with water and optionally centrifuging several times; vii) drying the solid from the previous step at a temperature in the range of from 100 to 150 ° C; (viii) The dried solid is ground to a powder and calcined at a temperature of at least 900 ° C for at least 2 hours. Method according to claim 1, characterized in that the surfactant is selected from the group of non-foaming non-ionic surfactants containing -OH or -NH ₂ end groups, comprising ethoxylated (C1 to Cl2) aliphatic alcohols, ethoxylated (C16 to C21) fatty acids, preferably (C16 to C18) fatty acids, polyoxyethylenes, carboxylic acid esters (C1 to C20), polyethylene glycol esters. Method according to either of Claims 1 and 2, characterized in that the surfactant is in the form of a 30 to 70% aqueous solution, preferably a 40 to 60% aqueous solution. Process according to any one of claims 1 to 3, characterized in that the water-soluble salts of cations A, B, C and D are selected from the group comprising salts of inorganic acids, organic monocarboxylic, dicarboxylic and tricarboxylic (C1 to C10) acids, and (C1). to C4) alkoxide salts, preferably the water-soluble salts of cations A, B, C and D are their sulfates, carbonates, halides, nitrates, phosphates, acetates, formates, citrates, oxalates, lactates, oxalates, ethoxides. The process according to any one of claims 1 to 4, wherein the water-soluble salt of the anion selected from carbonate, bicarbonate, oxalate, sulfate, metaphosphate, phosphate, hydroxide, nitrite, chromate and dichromate in step i) has a cation selected from the group consisting of Na ⁺ , K ⁺ , NH ₄ ⁺ . - 13 GB 307189 B6 Process according to any one of claims 1 to 5, characterized in that the step of drying the solid phase in step vii) is carried out at a temperature of 120 ° C. Process according to any one of claims 1 to 6, characterized in that the calcination in step viii) is carried out at a temperature in the range from 900 ° C to 1000 ° C. Eighth catalyst of the perovskite structure of the general formula A] _x B _x C _y O _y Di _ _{3 with} high-temperature decomposition of N ₂ O, wherein A and B are selected from the group consisting of lanthanide metals, alkaline earth metals, metals of Group IV and II1.A .A, Group IB, II.B, II.B, IV.B, VI.B, VIII.B and Bi transition metals; C and D are selected from the group consisting of transition metals of Group IV.B, Great, VI.B, VII.B, VIII.B, lanthanides, Sn, Al and Sb; and wherein x and y are independently numbers in the range of 0 to 1 and δ is a number indicating the non-stoichiometry of oxygen, ranging from -0.1 to 0.5; and wherein the compound of formula A | _X B _X C _V D | _In O _{3 δ} is not BaMnO ₃ , CuMnO ₃ , YCoO ₃ , CeCoO ₃ , LaSbO ₃ , YosSro 5MnO ₃ , MgTio, ₂ MnO0 ₃ , Ceo ^ Sro ₃ MnO ₃ , TIVO ₃ , Lao jSro ^ FeOs, CaTiosCeo _{> 2} 0 ₃ , Cao 7Ceo _{> 3} Mn0 ₃ , AgCeo ^ Mn _{δ 3} , Pbo, ₂ Lao, 8Mo0 ₃ . 9. A catalyst as the perovskite structure for high temperature decomposition of N ₂ O according to Claim 8, characterized in that it is selected from the group consisting of Sr, Lao _{i5 0>} 5Mn0 ₃ Lamna ₃ Zno.sCuo.sAIOs, Cao_7Cuo _J3 Mn0 ₃ Zno.sSro Ceo ^ ^ ^ Oi Well, ZrO ^ ^ Coo CEOs, Lage Feo ^ ^ Os Cro.8Nio _j2 CE0 _3, MgO-SnO Ltd. _{5 3} PbTiooMno ^ Oi, Ceo, 5Sro, 5Zr0 _3, MgO-Cdo 5WO _third Use of perovskite structure catalysts of the general formula A _n B _m C _o D _p Z _q O ₃ according to claim 8 or 9 for high temperature decomposition of N ₂ O.